화학공학소재연구정보센터
Macromolecules, Vol.43, No.17, 7269-7276, 2010
Effect of Grafting Density on Phase Transition Behavior for Poly(N-isopropylacryamide) Brushes in Aqueous Solutions Studied by AFM and QCM-D
The effect of grafting density on the phase transition behavior of poly(N-isopropylacrylamide) (PNIPAM) grafted onto a flat substrate was investigated using an atomic force microscope (AFM) and a quartz crystal microbalance (QCM-D). We prepared PNIPAM brush layers at three different grafting densities on silicon wafers using a "grafting from" atom transfer radical polymerization (ATRP) approach. AFM imaging in water at various temperatures showed that the transition behavior of the grafted PNIPAM chains from a brush-like to a mushroom-like morphology was dependent on the grafting density: the images change abruptly from essentially featureless to domain structures across the LCST for the low-density surface, whereas the change in the images becomes less abrupt with increasing polymer graft density. The QCM-D data also indicated a significant dependence of the layer properties on the grafting density, confirming the behavior differences suggested by the A FM images. In particular, the dissipation data strongly suggest that the magnitude of lateral aggregation for the PNIPAM chains depends on the grafting density. A similar effect of grafting density was also observed for the phase transition as a function of salt concentration in sodium sulfate solutions.